Chelating polymers and method of preparation



3,395,134 Patented July 30, 1968 3,395,134 CHELATING POLYMERS AND METHOD OF PREPARATION Gaetano F. dAleiio, South Bend, Ind., assignor, by direct and mesne assignments, of seventy-five percent to Gaetano F. dAlelio, South Bend, Ind., and twenty-five percent to Walter J. Monacelli, Cleveland, Ohio No Drawing. Continuation-in-part of applications Ser. No.

28,560 and Ser. No. 28,563, May 12, 1960. This application May 14, 1964, Ser. No. 367,546 8 Claims. (Cl. 260-895) ABSCT OF THE DISCLOSURE This invention comprises a chelating polymeric structu're having at least 0.1% of a repeating unit of a formula selected from the class consisting of t CH2([3- o 0 (CHR),.'N(OHRC 0 0M), -CHZC o oNR'wHRn'NwHRo o OM);

wherein R, R, and n and M are as defined hereinafter but are illustrated by repeating units having the formulas CHz(|3H- O ONHCH CHzN(CH2COOM)g CH2CH-- C O O OHzCH N(OHaCOOM)2 (I311: CH2(IJ o o 0 011 0113) CH N(CH;COOM)g r CHzC- boo CH2CHzN(CH2COOl\/I)g CH2CH OONHN(GHZC O QM)2 wherein M can be hydrogen, alkyl, aryl, ammonium and metal as more specifically defined hereinafter.

This application is a continuation-in-part of applicants copending applications Ser. No. 28,560 and Ser. No. 28,563, both filed May 12, 1960, and both now abandoned.

This invention relates to the production of new chelating polymers and a new process for preparing chelating polymers. Generally, it is concerned with crosslinked polymers having pendant coordination groups attached to the chain and to the process of preparing such polymers. It also deals with the grafting of monomers containing coordination groups to preformed polymers.

One object of this invention is to provide an improved and economical method of preparing chelating polymers.

Another object of this invention is to prepare chelating polymers with good physical properties.

A further object of this invention is to prepare such chelating resins from many well-known and available commercial non-chelating polymers.

A still further object of this invention is to tailor-make new chelating resins.

Further objects and advantages of this invention will becgme apparent as the description of the invention procee s.

The objects of this invention have been achieved by grafting specific monomers having at least one unsaturated polymerizable ethylenic group and at least one coordination moiety to a preformed polymer. Such monomers may be termed coordination monomers or monomeric ligands. By a monomeric ligand is meant a monomer having (1) at least one vinyl or vinylidene group, and (2) at least one other group containing two atoms such as' nitrogen or oxygen which can act as donors to a metal ion. If these donor atoms are spacially located in the moiety so that on reaction with the metal ions a five or six membered ring can be formed, such monomers are known as chelating monomeric ligands. Suitable chelating monomers which can form chelating structures are the amino-acetic derivatives. A typical example is B-acryloxy-N-ethyl amino diacetic acid CH =CHCOOCH CH N(CH COOH 2 which when polymerized alone produces a chelating polymer, also termed a polymeric ligand. When copolymerized with a crosslinking monomer, an infusible polymeric ligand is obtained. The full efficiency of such polymers, though high, is not fully realized because of partial entanglement of the chelating moieties in the polymer network. This eificiency can be improved if more of the chelating functions could be exposed. One possible method of reducing the entanglement is to attach the chelating structures to a preformed polymer, such as by grafting. The fact that a certain monomer is a chelating monomer, is no assurance that when grafted to preformed polymer, that the grafted polymer will act as a chelating polymer. It has already been pointed out (H.P. Gregor, M. Taifer and E. 1. Becker, Industrial and Engineering Chemistry, 44 2834 (1952) in the process of preparing a chelating polymer that the chelating function should not be altered by the polymerization reaction and that both arms of the chelate structure should be in the proper spacial arrangement. A convenient process for grafting a monomer to a polymer is by means of ionizing radiation.

One method (A) of grafting a monomer to polymers is to mix or impregnate a polymer M with the monomer, B, and then irradiate the mixture. In this process, the monomer, B, may form some homopolymer which may introduce problems due to solubility and swelling of the homopolymer, but this can be eliminated by using with the coordination monomer, B, a small amount of a crosslinking monomer such as divinylbenzene and others to an amount of 0.1% to 20% based on the coordination monomer, to give lower swelling potentials, greater toughness of the polymer, etc. Besides divinylbenzene, many other crosslinking agents can be used, a few illustrative examples of which are liquid and low molecular weight polybutadiene, divinylnaphthalene, vinyl isopropenyl benzene, diallyl benzene, etc.; the polyunsaturated esters such as ethylene glycol diacrylate, ethylene glycol dimethacrylate, trimethylene glycol dimethacrylate, diallylitaconate, glycol maleate, etc.; diallyl succinate, divinylphthalate, diallyl maleate; the polyunsaturated ethers such as divinyl ether, trimethylene glycol divinyl ether, etc., vinyl-phenylacrylate, 2-isopropenyl-5-acryloxy naphthalene; vinyl-3 ,S-diallyloxy-palmitate, etc.

Another method (B) of grafting a coordination monorner to a preformed polymer comprises irradiating the preformed polymer in the presence of oxygen or air to form polymer hydroperoxides and diperoxides. Such polymeric peroxides are relatively stable at ordinary temperatures but decompose at high temperatures to form macroradicals. If the decomposition is performed in the presence of a monomer, then crosslinked graft copolymers are obtained. For example, when a polymer obtained from monomer M is irradiated in the presence of oxygen, there is obtained a peroxidized polymer which contains also crosslinkages and frozen free radicals, thus -MM-M-ir-M-M-MM-M-1ir-M Then a monomer, B, is grafted to the polymer, and there is obtained a grafted polymer, thus Usually, the type of monomer used in normal grafting is a simple monomer such as styrene, methyl acrylate, methyl methacrylate, etc. which do not have to perform, after grafting, complicated functions such as chelation. When a chelating monomer such as CHzC O OH CH;=CHC O O CH CH N CHgOOOH is used in a grafting process, there can be no assurance that the resulting grafted product will be chelating polymer since changes can be rendered by the process in the structure as pointed out by Gregor et al.

Thus, if the polymer M is polyethylene and the monomer, B, is acryloxy-ethyl im inoacetic acid and this monomer is impregnated into the polyethylene, there is no as surance that on irradiation an efficient chelating polymer will be obtained. The object of this invention accordingly is to prepare chelating polymers by grafting by methods which involve the use of radiation.

Thus, when the polymer M is polyethylene, and the monomer, B, is acryloxy-ethyliminoacetic acid, there is obtained an infusible, graft chelating copolymer having pendant chelating groups to the polyethylene chain, thus The term irradiation as used herein, means high energy and/ or the secondary energies resulting from conversion of this electron energy to neutron or gamma radiation, said electron energies being at least 100,000 electron volts. While various types of irradiation are suitable for this purpose, such as X-ray and gamma and beta rays, the radiation produced by high power electron linear accelerators has been found to be very conveniently and economically applicable and to give very satisfactory results. However, regardless of the type of irradiation and the type of equipment used for its generation or application, the use thereof in the production of polymer materials as described herein is contemplated as falling Within the scope of this invention, preferably that produced by or from electron energy of at least about 100,000 electron volts. While there is no upper limit to the electron energy that can be so applied advantageously, the effects desired in the practice of this invention can be accomplished without having to go above 50,000,000 electron volts. Generally, the higher the electron energy used, the greater is the depth of penetration into the (massive structure of the polymer or polymenizable materials, and the shorter is the time of exposure required to accomplish the desired result. For other types of irradiation, such as gamma and X-rays, energy systems equivalent to the above ranges of electron volts are desirable.

It is intended that the term irradiation include what has been referred to in the prior art as ionizing radiation which has been defined as radiation possessing an energy at least sufiicient to produce ions or to break chemical bonds and thus includes also radiations such as ionizing particle radiation, as well as radiations of the type termed ionizing electromagnetic radiation.

The term, ionizing particle radiation, has been used to designate the emission of electrons or highly accelerated nuclear particles such as protons, neutrons, alphaparticles, deutrons, beta-particles, or their analogs, directed in such a way that the particle is projected into the mass to be irradiated. Charged particles can be accelerated by the aid of voltage gradients by such devices as accelerators with resonance chambers, Van de Graalf generators, betatrons, synchrotrons, cyclotrons, etc. Neutron radiation can be produced by bombarding a selected light rnetal, such as beryllium, with positive particles of high energy. Particle radiation also can be obtained by the use of an atomic pile, radioactive isotopes, or other natural or synthetic radioactive materials.

Ionizing electromagnetic irradiation is produced when a metallic target, such as tungsten, is bombarded with electrons of suitable energy. This energy is conferred to the electrons by potential accelerators of over 0.1 million electron volts (mev.). In addition to radiations of this type, commonly called X-rays, an ionizing electromagnetic radiation suitable for the practice of this invention, can be obtained by means of a nuclear reactor (pile) or by use of natural or synthetic radioactive material, for example, cobalt 60.

Various types of high power electron linear accelerators are commercially available, for example, from Applied Radiation Corporation, Walnut Creek, Calif. In the following Example I, the Arco type travelling wave accelerator, Model Mark I, operating at 3 to 10 million electron volts, was used to supply the irradiation. Other types of accelerators, such as supplied by High Voltage Engineering Corporation, Burlington, Mass, or as described in United States Patent 2,763,609 and British Patent 762,953 are satisfactory for the practice of this invention.

oftentimes, the radiation doses are reported in megareps, which represent 1,000,000 reps. A rep is defined, according to Reactor Shielding Design Manual, edited by Theodore Rockwell III and published by D. Van Nostrand Company, Inc., 1st edition, 1956, as that radiation dose that produces energy absorption in human tissue equal to 93 ergs per gram of tissue.

It is recognized that the energy characteristics of one form of ionizing radiation can be expressed in terms which are appropriate for another form. Thus, one may express the energy of either the particles of radiation commonly considered as particle radiation or of the photons of radiation commonly considered as Wave or electromagnetic radiation in electron volts (ev.) or million electron volts (mev.). In the irradiation process of this invention, radiation consisting of particles or photons having an energy of 50 ev. and over may be employed and particles or photons having an energy of 0.001 mev. and over are preferred. With radiation of this type, attachment of an unsaturated ligand or chelate to an organic polymer can be obtained with a minimum length of exposure to the radiation permitting maximum efiiciency in utilization of the radiation. Particles or photons with an energy equivalent over 0.1 mev. up to 2 to 5 mev. are the most useful from a practical standpoint, although radiation with energies of 10 mev. and higher may be employed. When grafting is accomplished by radiation organic polymer chosen as the sub strate for the graft polymer is exposed to at least 0.01 watt-sec/cm." of ionizing radiation whether the grafting is done by method A or B given above. When the polymer is peroxidized by irradiation prior to grafting with monomer, the irradiation of the polymer is performed in the presence of small amounts of oxygen such as about 1 X 10 molecules of oxygen per cm. of polymer substrate up to the concentration found in normal air or modified by the addition of oxygen, or even pure oxygen. Also, mixtures of oxygen and inert gases such as helium and argon can be used.

The coordination monomers used in the practice of this invention are the new monomers selected from the class having the general formulas R R 01-1,:(3-0 Ol IN(CHRC 0 OM),

and

R (1112:27-0 OY(CHR)HIN(CHR'CO OM)2 wherein:

R represents H, CH Cl and CN;

R represents a lower alkyl or aralkyl group;

Y represents 0 and NR;

n represents a numerical value of at least 2 and no more than 10.

M is a member of the group consisting of hydrogen, ammonium bases, lower alkyl and lower aryl groups, and metals. The ammonium bases are the ammonium radical and derivatives thereof in which the substituent groups are alkyl and aryl groups preferably of no more than carbon atoms.

Illustrative examples of such monomers are:

CH2=CHGONHN(CH2O O OM) (3H3 oHi=c ooNnN ornoooM)2 CHFCHCON(CHa)N(CHzCOOl\/l) oHFoHo o o omcmmomo 0 0M (3H3 CH2=CC o 0 ornommorno 0 on :1 on,=c-o 0 o omcmornmomo 0 0M ON (3H3 oHFh-oooonommomoooMn 011250150 0 o (CH2)uN(CHzC 0 0M om=o (CH3) 0 0 o omnmomo 0 0M om=o cm) 0 o o onnmmomo o 0M 2 CHFCHGOO CH2CH2N(CHCOO1VI)2 CH2=C 011. o 0 ON(C10H21)CH2CH2N(C}I2C 0 OM)2, etc.

These monomers all contain the chelating function N(CHRCOOH) and may be considered derivatives of the amino acids H-N(CHRCOOH) from which they can be prepared; or they can be considered as acryloxy substituted compounds of derivatives of the imino acids such as the hydrazine diacetic acids,

H-NN(CHR'COOH) the omega-hydroxy alkyl imino diacetic acids,

HO(CHR),,N(CH COOH) and the omega-aminoalkyl imino diacetic acids,

HN (CHR) N (CH COOH) As used herein, the term lower alkyl, is intended to include such groups having no more than about 10 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, secondary butyl, amyl, secondary amyl, hexyl, heptyl, nonyl, decyl, secondary hexyl, secondary nonyl, benzyl, phenethyl, dimethylphenethyl, ethylphenethyl, propylphenethyl, butylbenzyl, etc. groups.

The ammonium bases defined herein for M include the ammonium radical and various substituted ammonium radicals having various substituents thereon, such as alkyl groups, aryl groups, hydroxyalkyl groups, etc., preferably those having no more than about 21 carbon atoms, advantageously those having no more than about 10 carbon atoms. Typical examples of such substituted ammonium radicals include those derived from ammonia, methyl amine, dimethyl amine, trimethyl amine, ethyl amine, diethyl amine, triethyl amine, propyl amine, butyl amine, dibutyl amine, tributyl amine, trihexyl amine, triheptyl amine, ethanol amine, diethanol amine, triethanol amine, isopropanol amine, diisopropanol amine, triisopropanol amine, methyl diethanol amine, dimethyl ethanol amine, morpholine, dimethyl benzyl amine, pyridine, ethyl pyridine, quinoline, isoquinoline, amino pyridine, guanidine, biguanidine, aniline, methyl aniline, dimethyl aniline, phenylene diamine, piperazine, triethylene diimine CHaCHz OIIzCHz hydrazine, methyl hydrazine, symmetrical dimethyl hydrazine, phenyl hydrazine, amino imidazole, amino diazines, hydrazino triazines, etc.

Typical metals that can be used in substitution for M in the formulas given herein, include lithium, sodium, potassium, rubidium, cesium, calcium, strontium, barium, and the chelate-forrning metals as disclosed in Chemistry of Metal Chelates by Martell and Calvin, published by Prentice-Hall (1956). Page 182 of this books shows the periodic classification of chelate-forrning metals.

The chelating monomers used in the practice of this invention are readily and econamically prepared from commercially available chemical intermediates. They can be prepared by reacting an acrylyl chloride,

in the presence of a hydrohalide acceptor (HAC), with (1) an amino-imino diacetic acid;

I HAG CHrCCOCl HNRM(CHRCOOH)2 I CHZ=C CONN(OHR'o0oH),

or for example NazCOs CH CHOCI HzNN(CH CO0H)2 CHFCHCONHNUJHZGOOHM or (2) an omega-hydroxy alkyl imino diacetic acid:

l HAO CHFCCOCI HO(CHR)nN(OHRCOOH) for example OH= C(OH 0 0 (CH2)N(OHgO0 OH),

or (3) with an omega-aminoalkyl iminodiacetic acid:

C1 CHz=( JCONH(CH2)2N(CHOOOH) The hydrazino-acetic acids are readily prepared by reacting the appropriate hydrazine with chloroacetic acid according to the method of Bailey and Read given in I. Am. Chem. Soc. 36, 1747 (1914) as illustrated by the equation:

from which the free acid crystallizes when the pH of the solution is adjusted to 4.

The omega-aminoalkyl iminodiacetic acids are readily prepared from the 'y, omega-diamines by the method of Moore, Boyle and Thorn given in J. Chem. 800., p. 39 (1929) whereby one amino group is first reacted with a chlorocarbonate and the second amino group is reacted with a haloacetic ester as illustrated by:

NH2(CH2)7N(GH2COOB3)2 i NH2(CH7)2N(CH2COOH)$ Alternately, the amino-derivative can be more readily prepared by treating an iminodiacetic acid alkali salt with an alkylene imine:

HzNCHR CHRNKJH C O N2.)

for example orig 0H, HN(CH COONa)n HzNCH CH N(OH2C0ONa) Some omega-hydroxy alkyl imino diacetic acids are commercially available such as HOCH CH N (CH COOH 2 Alternately, these compounds can be more readily prepared by reacting an alkylene oxide with an imino acid:

HO CHRCHR'N(CHRC O ONa);

for example (EIz/CHCHa HN(CH2COONa)g The monomers of this invention can be polymerized individually or as mixtures with each other, or with 0.1, preferably 1 percent by weight or more of other vinyl and vinylidene compounds, such as styrene, alphamethyl styrene, vinyl toluene, vinyl xylene, chlorostyrene, butadiene, isoprene, acrylonitrile, methacrylonitrile, methacrylate, ethylacrylate, benzylacrylate, methyl methacrylate, ethyl methacrylate, glycol diacrylate, glycol diacrylate, glycol dimethacrylate, allyl acrylate, allylmethacrylate, vinyl acetate, vinyl propionate, diallyl succinate, diallyl phthalate, maleic anhydride, dimethyl maleate, itaconic anhydn'de, itaconic imide, dimethyl itaconate, diallyl itaconate, acrylamide, methacrylamide, allylacrylamide, hydroxyethylacrylamide, N-methylene-bisacrylamide, acetylglycine, vinyl pyridine, methacrylyllysine, methylvinylketone, acetylaminophenylethylene, vinylimidazole, 2-isopropenyl-4risopropyl 2-oxazolin-5- one,N-viny1-5-methyl-2-oxazolidinone, N-vinyl pyrrolidone-2, etc. or they can be grafted to other polymers containing peroxy groups to produce grafted copolymers, as disclosed in my copending application, Ser. No. 28,560, and now abandoned, filed the same date herewith.

When large quantities of the order of 99.9% of a nonchelating monomer such as styrene, methyl methacrylate, etc. are used, improved adhesion of such polymers to metal sulfates is obtained, and this improvement is attributed to chelation of the imino-diacetic acid groups contained in the copolyqmer with the metal surface.

The polymers and copolymers of this invention can be prepared in mass, in solution, in suspension, and emulsion systems, using the accepted initiating systems, such as the per compounds that generate radicals, or thermally, or with ultraviolet light, or with ionizing radiation, and in some cases, with ionic catalysts, both cationic and anionic, e.g. BF sodamide, HF, etc.

In the practice of my invention, I have also discovered an improved and economical method for the grafting of monomers, including coordination monomers, to crosslinked, peroxidized polymers which. comprises impregnating the peroxidized polymer with the monomer and thereafter effecting the grafting in a non-reactive liquid media in which the polymer is insoluble. For example, by irradiating polyethylene beads in the presence of oxygen in a tumbling barrel with an electron beam, there is obtained a crosslinked, peroxidized polyethylene. These beads then are immersed in a 50% ether solution of the dimethyl ester of acryloxyethyliminoacetic acid, the swollen beads separated from the solution, the ether evaporated from the beads, the beads dispersed in water, preferably with a small amount of interfacial or dispersion agent, and graft polymerization achieved by heating while the dispersion is agitated. By this process, sticking and agglomeration is avoided and tough, resilient, nonfragile chelating polymers are obtained. In those cases where the monomer is an active swelling agent for the polymer, the use of auxiliary swelling agents is not necessary, while in other cases where the boiling point of the swelling agent is higher than about 50 C., as for exexample, benzene or toluene, it is not necessary to remove it from the swollen polymer before grafting the monomers, and in the case of the low boiling swelling agents, if the grafting of the monomer is accomplished under pressure, it becomes unnecessary to remove the swelling agent unless desired.

The organic polymers suitable for grafting include any normally solid organic polymeric material, particularly those with molecular weights in excess of 500 and es pecially in excess of 2000. The polymers may be oriented or unoriented. Thus, there may be employed hydrocarbon polymers, such as polyethylene, polystyrene, polybutadiene, rubber, polyisobutylene, butadiene-styrene copolymers and the like; halogenated hydrocarbon polymers such as polyvinyl chloride, polyvinylidene chloride, polychloroprene, polytetrafiuoroethylene, polyvinyl fluoride and the like; ester-containing polymers such as polyvinyl acetate, polymethyl methacrylate, polyethylene terephthalate and the like; hydroxyl-containing polymers such as polyvinyl alcohol, cellulose, regenerated cellulose and the like; ether-containing polymers such as solid polytetrahydrofuran, dioxolane polymers and the like; condensation polymers, such as phenol-formaldehyde polymers, ureaformaldehyde polymers, triazine-formaldehyde polymers, polyamides, polyimides, and the like; polyacrylonitrile, polyvinyl acetals and mixtures or copolymers based on two or more of the above compounds, as well as natural polymers, such as cotton, wool, silk and the like.

The shape of the organic polymer employed as a substrate in the present invention is not limited or critical. Also, it may be a film, molded, object, fiber, knitted or Woven fabric, tube, pipe, beading, tape, extruded molding, wire covering, powder or the like. Of particular advantage are films, fibers, fabrics, and various extruded forms since they are readily adapted to continuous op- 19 eration according tothe process of this invention. Shaped polymers in these forms may be unrolled or extruded into the path of ionizing radiation and then either run sub stantially immediately into contact with the polymerizable monomer or wound up and contacted with the polymerizable monomer in a separate treatment.

The chelating polymers prepared by the process of this invention are .useful in the recovery of and the separation of metals which form-chelatesThese are disclosed in Chemistry of Metal Chelates by Martell andCalvin, published by Prentice-Hall in 1956. Page 182 of this book has a table showing the periodic classification of chelate forming metals. T hose metals for which the process of this invention is particularlyappropriate are those-of groups-III and IV of the periodic table-having atomic weights of at least 80,- as well asmagnesium and the metals of group VIII. This invention is very useful in recovery ofrare earths or la'nthanides, and-the actinides sincethey are generally found in very dilute concentrations and' generally' are otherwise very difiicult to recoverfand separate. Specific'metals for which this process is particularly appropriate include aluminum, titanium, vanadium, silicon, chromium, manganese, iron, cobalt, nickel, copper, zinc, magnesium, gallium, germanium, arsenic, ytterbium, zirconium, columbium, technetium molybdenum, ruthenium, rhodium, palladium, silver, cadmium, indium, tin, antimony, hafnium, tantalum,tungsten, rhenium, osmium, iridium, platinum, gold, mercury, thallium, lead, bismuth, scandium, lanthanum, thorium, uranium, plutonium, etc.

While reference is sometimes madeherein to recovery of the metal, it is intended to include recovery of the metal in the cationic form or in the form of its compound, or in accordance with whatever manner the metal exists in the chelate form and the'state in which it is subsequently removed from thechelated polymer.

The following examples are given to. illustrate better various methods for the practice of this invention and are not intended in any way as a limitation on the methods of practicing the invention. Parts and percentages are by weight unless otherwise indicated.

EXAMPLE I I A spool containing .1000 grams of 400'denier polyethylene filament is irradiated by running the filament through a radiated field in air at, room temperature to a megarep dose. The filament then is immersed in a 50% mixture of a l CH =CHCOOCH CH N (CH COOH) 2 and ethyl acetate and heated to 50 C. until the increase in weight of the filament is about 45%. The filamentthen is washed in acetone to remove unreacted monomer and the grafted copolymer hydrolyzed at 80 C. in a 10% sodium hydroxide alcoholic solution followed by washing a with water to remove free sodium hydroxide. The filamentary chelating polymer is passed through a liter of 3% sodium chloride solution containing 1% of'cupric ions as the chloride. As the polymer reacts with the copper ion it becomes blue in color, the copper being exhausted substantially from the solution when less than 50% of the filamentary polymer is passed through the solution. The exposed portion of the filament is washed with water until free of sodium chloride and then immersed in 2 N hydrochloric acid from which water and excess hydrochloric. acid are recovered by evaporation, leaving substantially pure cupric chloride as a residue.

By substituting other acids for the hydrochloric acid in the recovery stage, such as .nitric, sulfuric, phosphoric, etc., copper nitrate, copper sulfate, copper phosphate, etc., is recovered instead of cupric chloride.

When a correspondingly larger amount of solution containing 0.1% cupric ion instead of 1% is used in this example, a similar recovery of metal is obtained. Substantially all of the metal is recovered also from similar solutions containing a lower concentration of copper ions, for example, in a 3% sodium chloride solution containing 250 parts per million, parts-per million, and 5 parts per million, respectively, of copper'ion. Recovery of copper also is obtained from solutions containing other alkali and alkali-earth salts such as potassium, lithium, magnesium, calcium, and strontium, such as their chlorides, nitrates, sulfates, phosphates, and acetates. Fo'r'example, all of the copper is recovered from a 15% calcium chloride solution having- 25 ppm. of copper ions.

' EXAMPLE II The procedure of Example I is repeatedwith co'baltic chloride solutions and the metal is recovered in a similar manner. During the process, the filamentary chelating polymer becomes red as itreactswith the cobaltions. When solutions of aluminum, cesium, lanthanum, chr0- mium, manganous, manganic, ferrous, ferric, nickel, zinc, cadmium, lead, platinum, palladium; canadium, tantalum, zirconium, titanium, and'uranium ions are used instead of copper or cobalt-ions, they are recoveredalso in a-similar fashion. a t

EXAMPLE III The procedure of Example I is repeated using a 3% NaCl solution containing 0.1% of cupric ion and 0.1% of cobalt ions. When the filamentary chelating polymer is drawn slowly through the solution, a blue color appears on the filament until almost all of the copper is coordinated, then the color becomes red until substantially all of the cobalt is coordinated. When the process is repeated in the absence of sodium chloride in the solution, an identical separation is obtained.

EXAMPLE IV The process of Example HI is repeated to recover and separate cobalt and nickel from the following solutions Sol. N 0. Salt Percent Percent Percent Cobalt Nickel EXAMPLE v The grafting procedure of Example I is repeated with OH =CHCONHCH CH N(CH COOH) as the monomer and is used for the recovery of metals according to the procedures of Examples I to IV inclusive.

EXAMPLE VI The grafting procedure of Example I is repeated using as the monomer CH3 Gupta-oooorL-ommofl ooorln CH3 and used for the recovery of metals by the procedures of Examples I to IV inclusive.

EXAMPLE v11 1000 parts of polyethylene granules are irradiated in air in a tumbling barrel at room temperature with a cobalt 60 source to a dose of 15 megareps and then immersed in a 50% of ICHs CH u-GOooHoH1N oH,oo0H

and heptane and heated at 6 0 C.70 C. until the increase in weight is about 15% and there is obtained a graft copolymer having chelating properties similar to the polymer of Example I.

EXAMPLE VIII The procedures of Examples I to VII are repeated with polypropylene and similar results are obtained.

EXAMPLE IX The procedures of Examples I to VII are repeated with a 90% ethylene-10% propylene copolymer with similar results.

EXAMPLE X The procedures of Example I to VII are repeated with a polymer of butene-l and similar results are obtained.

EXAMPLE XI The procedures of Example I to VII are repeated with polyacrylonitrile and coordination polymers are obtained and used with similar results.

EXAMPLE XII The procedures of Examples I to VII are repeated with unplasticized polyvinyl chloride using 10% by weight of divinylbenzene based on the grafting monomers and similar results are obtained.

EXAMPLE XIII The procedure of Example VII is repeated with 6-6 nylon containing divinylbenzene with similar results.

EXAMPLE XV The procedure of Example VII is repeated with polycaprolactan containing 5% diallyl maleate with similar results.

EXAMPLE XVI The procedure of Example VII is repeated with polytn'fiuorovinyl chloride-perfluoro propylene copolymer using by weight of divinylbenzene based on the grafting monomer and similar results are obtained.

EXAMPLE XVII The procedure of Example XIII is repeated using polydimethylsilicone and with similar results.

EXAMPLE XVIII groups. When packed in a column they are shown to be effective chelating polymers for iron, nickel, cobalt, zirconium, and copper.

EXAMPLE XIX The procedure of Example I is repeated using instead of a copper solution, an 8% NaCl solution containing 0.1% MgCl and the MgCl' is extracted from the solution, with similar results.

12 EXAMPLE XX Example I is repeated with a series of coordination polymers prepared by the grafting of 10, 25, 50, 75, 100, 150, 150, 250, and 300% respectively of on the polyethylene, and (a) copper recovered substantially quantitatively from a 3% sodium chloride solution; (b) zinc recovered substantially from a 10% K 50 solution containing 0.5% zinc chloride.

EXAMPLE XXI The procedures of Example XX is repeated using polyethylene monofilaments of 50, 100, 250, 500, 750, 1020, 1330, 4380, 7600, 13,565 denier with similar results.

EXAMPLE XXII The procedure of Example XXI is repeated using, instead of monofilaments, a number of twisted polyethylene multifilaments, namely, (a) two S-thread 500 denier line, (b) a 6-thread 1200 denier line, (0) a 10-thread 4500 denier line, (d) a IS-thread 7500 denier line, and (e) a ZO-thread 15,000 denier line, with similar results.

EXAMPLE XXIII A 7-strand stainless steel wire of 0.15 inch diameter is extrusion-coated with 5 mils of high density polyethylene (0.935) and from the 25 mil reinforced polyethylene a coordination polymer is prepared and used as in the procedure of Example I, and similar results are obtained. Instead of the 7-strand wire, a single wire of corresponding diameter is used to produce a stiffer product, and a larger number of strands is used to produce a more flexible product.

EXAMPLE XXIV A hollow polyethylene monofilament (4.5 millimeters outside diameter and 2.5 millimeters inside diameter) is treated by the procedure of Example I and there is obtained a hollow linear coordination polymer of greater buoyancy. When this polymer is used in recovering the copper by the procedure of Example I, the cobalt of Example III, and the zinc of Example V, identical results are obtained as when the solid polymers are used. By pinching and heat-sealing the hollow monofilament at regular 36-inch intervals along its length, air is sealed within the tube. If, instead of air, another gas, such as nitrogen, helium, or argon is used during the extrusion of the polymer, it may also be sealed within the hollow filament by heat-sealing the tube at desired intervals. The hollow-filamentary coordination polymer also may be filled with a liquid such as a medium viscosity mineral oil or silicone oil.

EXAMPLE XXV The procedure of Example XXIII is repeated using, instead of wire as the reinforcement, a rope of polyacrylonitrile coated with polyethylene and similar results are obtained. Also, instead of polyacrylonitrile, monofilaments, or spun yarn, thread or rope of cotton, linen, jute, hemp, rayon, nylon, polyethylene terephthalate, polypropylene, polyvinylfluoride, polyvinylchloride, and many other natural and synthetic polymers are used as the reinforcement for the grafted coordination polymers of this invention.

EXAMPLE XXVI A plastisol is prepared from 1000 parts of polyvinyl chloride, 50 parts of commercial divinylbenzene and 800 parts and formed into a 500 denier monofilament, following which it is subjected to 30 megarep of irradiation from a Van der Grafif accelerator as in the procedure of Example I to give a crosslinked grafted coordination polymer having coordination activity similar to the polymer of Example I.

of Example I.

13 EXAMPLE XXVII A polyethyleneterephthalate yarn of 140' denier, 46 filaments is immersed in a 50 percent dioxane solution of CH CHCOOH CH N(CH COOH) containing 1% of diyinylbenzene for 48 hours. After eliminating the excess liquid by twisting, the yarn is wrapped in aluminum 'foil and subjected to irradiation of a resonance transformer with anemission current of 560 microamperes at 1 mev. until a dose of 25 mrep is reached, and there is obtained a coordination polymer with the propertiessimilar to that EXAMPLE XXVIII A spool of polypropylene ribbon 0.250 wide and 0.010" thick is treated according to the process of Example I and similar results are obtained.

.EXAMPLE XXIX Three hundred parts of a 100 filament 250 denier polyethylene terephthalate yarn isvarnish coated with a 30% .dioxauesolution of a copolymer of 200 parts ethylacrylate and 162 parts of CH CHCOOCH CH COOCH CH N(CH COOH) and dried and cured at 80 C. for 24 hours and then irradiated to megareps as in Example XXVI, and there is obtained a reinforced coordination polymer which coordinates readily with the ions of Hg, Cd, Zn, Cu, Ni, Co, Fe, Mn, Ag, Pb.

EXAMPLE XXX Examples I to XXI are repeated but instead of irradiating the polymers in air and then grafting the monomer to the polymers, the polymers are first immersed in a dioxane or acetone solution with or without 1% divinyl benzene of the various chelating monomers for 48 to 192 hours; then after removing the excess liquid by centrifuging, the swollen polymers are subjected to irradiation as in Example XXVII and coordination polymers with properties similar to those found in Examples I to XXI are obtained.

EXAMPLE XXXI To a mixture of 167 parts of HOCH CH N(CH COO H) 59 parts of trimethylamine in 500 parts of diethyl ether is added slowly in a reaction flask suitably equipped, 104.5 parts of methacrylyl chloride in 200 parts of ether at 25-30 C. After the addition of the acid chloridethere is added 0.25 part of tertiary butyl catechol and the reaction continued under, a nitrogen atmosphere for 46 hours. The precipitated trimethylamine hydrochloride is removed by filtration and 300 parts of water added to the reaction mixture, the ether removed by distillation leaving a water solution containing which can be used as such or purified further to isolate the pure compound. A convenient method of isolating the pure compound is to convert the monomer to a metal chelate. To part of the above solution there is added suificient NaOI-I to produce the salt,

CH CH =l-COOCH2OHzN CHzC O ONa):

of Cu(NO to produce CH2 CHFCC O O CHzCH NKJHzC O OhCu and by concentration of the solution there is isolated the solid crystalline CH3 I in solution and to this there is added an equivalent amount (3H3 0H=C000onlommomoooml A simple way to isolate the monomer in the free acid form is to treat the copper chelate of this'example in water with hydrogen sulfide. Thus r oHFo-oo o crucrnmomoo 0H 15' CuS and to remove the CuS by simple filtration leaving and isolating the monomer by concentration and evaporation of the aqueous solution. By either of these methods there is obtained the monomer (3H3 CHFCCOOCH2CHzN(CHgCOOH)r which on elemental analysis gives values of 49.2% C; 6.08% H; and 5.75% N, which are in good agreement with the theoretical values of 49% C; 6.13% H; and 5.7% N.

EXAMPLE XXXII By using the procedure of Example )QH, methacrylyl chloride is reacted with the following substituted iminodiacetic acids in the quantities indicated:

138 parts H NN(CH CO0H) 166 parts H NCH CH N(CH COOH) 236 parts HN(CH )(CH N(CH COOH) 222 parts H N(CH N(CH C0OH) and parts CH; HOCHQCHQN(CHOOOH 209 parts CH3 HooHr0H2oHzN(m :Ho0oH)a and the corresponding monomers having the acrylyl CH3 CHz=( JOO replacing the terminal active amino or alcohol hydrogen are obtained,

EXAMPLE XXXIII The procedures of Examples XXXI and XXXII are repeated using instead of methacrylyl chloride, the following chlorides in the amounts indicated:

90.5 parts CH =CHCOC1; 104.5 parts Cl CHg=C-C 0 Cl and 129.5 par-ts CN CH2=$-C 0 Cl and the acrylo-, a-chloroacrylo-, and a-cyanoacryloderivatives of the hydroxyalkyl-, the amino-, and the aminoalkyl-iminodiacetic acids are obtained in good yields.

15 EXAMPLE XXXIV This example illustrates the homopolymerization of the monomers of this invention. In a nitrogen atmosphere, thirty (30) parts of are added to 70 parts of deoxygenated distilled water containing 0.6 part sodium bisulfite. There is then added 0.9 part of ammonium persulfate in 5 parts of water and the mixture stirred at 60 C. for 8 hours producing a viscous clear solution of the polymer. Polymerization is also achieved in this same manner with the salts of the other monomers of Examples XXXI and XXXII.

Instead of the salts, the free acids also may be. homopolymerized by this procedure, or in solution in alcohol, or mixtures of alcohols and water, etc.; with other free radical-generating catalysts such as hydrogen peroxide, benzoyl peroxide, etc., alone or in a redox system. Also, these monomers may be homopolymerized or copolymerized by subjecting them alone or in admixture with other monomers or with solvents directly to ionizing radiation.

EXAMPLE XXXV To 100 parts of distilled water containing one part of dodecyl benzene sulfonate is added 25 parts of styrene and 12 parts of CH =CHCONHN(CH COO) Cu and .two parts of 50% H and one part of ferrous sulfate.

EXAMPLE XXXVI To a mixture of 90 parts of ethyl methacrylate, 5 parts of styrene and 5 parts of and 400 parts of ethyl acetate is added 2 parts of benzoyl peroxide and the mixture refluxed for five hours, then an additional 0.2 part of benzoyl peroxide is added, the mixture refluxed for 3 more hours and there is obtained a copolymer solution useful as a lacquer coating especially for metals. Sheets of aluminum, copper, and iron are coated with this solution, allowed to air dry, and then heated at 60-100 C. for 2 hours to eliminate residual solvent. The adhesion of the filmto the metal is much greater than when the chelating monomer is omitted from the formulation. The copolymer of this example may be used as the protective coat or it may be used as an undercoat for other coatings such as varnishes, paints, and lacquers. Improved adhesion is also found when only 0.1% of the chelating monomers of this invention, such as the monomer of this example or the monomers of Examples XXXI, XXXH, and XXXIII, based on the total weight of monomersin the copolymer are used in the preparation of copolymers.

The chelating polymers of this invention may also be prepared by first polymerizing or copolymerizing the EXAMPLE XXXVII Ten parts of styrene, 1.1 parts of commercial divinyl benzene (containing approximately 50% DVB-50% ethyl styrene, 45 parts of acrylyl chloride, 1 part of u,a-azobisisobutyronitrile are heated at 45 C. for 12 hours, 60

q 1 p C. for 18 hours, C. for 18 hours, and 100 C. for 24 hours, following which the hard copolymer is ground in a dry atmosphere to small granules and washed with five 100 part portions of dry heptane and then added to 100 parts of dry heptane, to which is added 50 parts of tertiary butyl hydroperoxide and 98 parts of tributyl amine and the mixture stirred for 24 hours at room temperature. The granules are removed by filtration and immersed in 5 portions of 300 parts of ethyl alcohol, filtered and dried at 3540 C. The peroxidized granules are added to 300 parts of water containing 3 parts of hydroxy apatite, 0.03 part of sodium dodecylbenzene sulfonate, 50 parts of out orr2=oHoooomonm dr1ooon i and 50 parts of benzene, and the mixture stirred for 36 hours at room temperature, followed by heating at 75- C. for 36 hours. The grafted granules were extracted with four 200 ml. portions'of methyl alcohol followed by refluxing in 1000 ml. of 5% NaOH for 5 hours and there is obtained a grafted copolymer having pendant structures attached. to the polymer with chelating properties similar to the polymer of Example I.

EXAMPLE XXXV III 100 parts of water, 1.10 parts of hydroxyapatite (0.005 to 0.2 micron size) 0.02 part of dodecylbenzene sulfonate, 0.2 part of benzyl peroxide, 1.4 parts of commercial divinylbenzene (approximately 50% DVB-50% ethyl styrene) 50 parts of styrene are mixed :at room temper ature and stirred to form a suspension system. A steady stream of air is passed into the dispersed system through a capillary for 2 hours, and with the air and stirring continued, the temperature is raised to 60 C. for 16 hours. Then the flow of air is terminated and the mixture heated to 80 C. for 18 hours. There are obtained crosslinked peroxidized beads. The suspension is cooled to 35 C., 25 parts of is added to the suspension, and the agitation continued for 2 hours followed by heating at 85 C. C. for 48 hours. The graft ester copolymer is treated with NaOH as in Example XXXI and :a chelatin-g copolymer with similar properties to the copolymer of Examples XXXVII is obtained.

EXAMPLE XXXIX Non-crosslinked copolymers and polymers also are made by post reactions. A copolymer of 20 parts of vinyl chloride, 20 parts of vinyl acetate and parts of acrylyl chloride prepared by heating the mixed monomers at 60 C. for 24 hours in the presence of 0.5 part of 'y,'y-azobisisobutyronitrile is reacted withtertiary butyl hydroperoxide as in Example XXXVII, cast into ribbon'of 10 mils wide and 1 mil thick and immersed in 20% aqueous solution of CH :CHCOONHCH CH N(CH COOH) and heated to 65 C. to a 20% Weight increase in the polymer, and there is obtained a polymer whose chelating properties closely resemble the properties of the polymer of Example I,

EXAMPLE XL A 30% solution of acrylyl chloride in tetrahydrofurane with 1% 'y,'y'-azobisisobutyronitrile on the weight of the monomer is heated at 75 C. for 48-72 hours, and then diluted to 10% solution with tetrahydrofurane. To this solution is added slowly an equivalent amount of NHZCHQCHZN (CH COOH) 2 as a 25% solution in tetrahydrofurane in the presence of suflicient solid NaHCO to produce the di-salt and the re- I 7 action continued at 50 C. for 12 hours. There is then added suflicient water to dissolve the polymer, producing a clear solution containing the polymer having repeating units of the formula:

which has marked chelating properties.

50 parts of distilled water, 0.5 part of hydroxy apatite (0.005 to 0.2 micron size), 0.1 part sodium dodecylbenzenesulfonate, 2.5 parts of commercial 50% divinylbenzene, 0.1 part benzoyl peroxide, and 35 parts of isopropyl styrene are mixed in a suitable reaction flask and stirred for 16 hours at 90 C., following which the mixture is cooled to 25 C. and 10 parts of cumene hydroperoxide added and the suspension heated to 35 -45 C. for hours. The beads are removed by filtration, washed with 3-100 part portions of methyl alcohol and 3-200 part portion of hexane and the beads reintroduced into the aqueous suspension system to which is added 50 parts of followed by stirring at room temperature for 24 hours, then at 80 C. for 72 hours to produce an infusible chelating polymer.

EXAMPLE XLI The procedure of Example I is repeated a number of times using in place of the grafting monomer therein, the respective monomers prepared in accordance with Examples XXXII and XXXIII. The resulting grafted copolymers have very good celating properties when tested as in Examples I-IV.

The polymers produced according to the processes described in the application and illustrated in the various working examples above have a plurality of repeating units which contribute chelating properties to the respective polymers. These repeating units can be linked directly in the linear chain of a polymer when the chelating monomer is homopolymerized or copolymerized with various monomers as discussed herein. In such case the repeating units can be interspersed with repeating units of the comonomers. These repeating units of the chelating monomers can be represented as present in the polymer molecule in the form of COO(CHR)n'N(CHRCOOM) wherein R, R, M and n are as previously defined. The radical (CHR'),,' is preferably (CH and advantageously has a total of no more than four groups representing lower alkyl groups in such radical.

When the chelating monomers are grafted onto a preformed polymer as described herein, the resultant c0- polymer has pendant radicals of one or more of the formulas:

wherein n is an integer having a value of at least one and the various other symbols have the definitions given above. Wherever n has been used in formulas hereinabove, it represents an integer having a value of at least 2. The end valence of the last repeating unit in a series can be attached to another polymer molecule or to a hydrogen atom or other chain terminating group.

The following typical repeating units illustrate those derived in the various polymers described in the working examples, as follows, including those in which metals have been added: 1

Examples I-IV CH2OH- COOCH2CH2N(GH2COOM) Example V CH2CH CONHCH2CH2N(CH2COOM)2 Examples VI-VII CH3 CHz( 3 C0OOH(CHa)CHzN(CHzCOOM) The repeating units of Examples I-V are attached to a preformed polyethylene. These same repeating units are also attached in other examples to various other preformed polymers: for example, on polypropylene in Example VIII; on an ethylene/propylene copolymer in Example IX; on polybutene-l in Example X; on polyacrylonitrile in Example XI; on polyvinylchloride in Example XII; on polytetramethylene-terephthalate in Example XIII; on 6-6 nylon in Example XIV; on polycaprolactam in Example XV; on polytrifiuorovinyl chloride-perfluoropropylene copolymer in Example LX; and on polydimethyl silicone in Example XVII.

Example XVIII shows the preparation of a copolymer having the repeating unit This same repeating unit is attached to various other polymeric materials as disclosed in Example XXV, for example, polyacrylonitrile, cotton, linen, jute, hemp, rayon, nylon, polyethylene perphthalate, polypropylene, polyvinyl fluoride, polyvinyl chloride, etc.

The homopolymer of Example XXXIV has a plurality of repeating units of the formula:

The styrene copolymer of Example XXXV has a plurality of repeating units of the formula:

CH2CH CONHN(CHCOOM)Z The terpolymer of Example XXXVI has repeating units of ethylmethacrylate, styrene and CH3 -onic- (1H3 COOCHzCHaCHzN CHCOOM The chelating effect of these repeating units is noted when as little as 0.1% by weight is present, preferably, however, at least 1% by weight is present.

In the above repeating units a preferred form is that in which M represents hydrogen.

While certain features of this invention have been described in detail with respect to various embodiments thereof, it will, of course, be apparent that other modifications can be made within the spirit and scope of this invention and it is not intended to limit the invention to 19 the exact details shown above except insofar as they are defined in the following claims. The invention claimed is: 1 1. A polymeric composition comprising in the polymer structure thereof at least 0.1 percent by weight of a repeating unit having a formula selected from the class consisting of: I

CH2C- ONN(CHR'COOM)1 i CH3C- OO(CHR)u'N(CHRCOOM) wherein:

R is a radical selected from the class consisting of hydrogen, methyl, chlorine and cyano; R represents a radical selected from the class consisting of alkyl and aralkyl groups having no more than 10 carbon atoms therein; n is an integer having a value of at least 2 and no more than 10; and M is a member of the class consisting of hydrogen and alkyl and aryl radicals each having no more than 10 carbon atoms, the ammonium radical and derivatives thereof in which each of the derivative groups is selected from the class consisting of alkyl and aryl groups having no more than 10 carbon atoms, and metal atoms. 2. The polymeric composition of claim 1 in which there is at least 1 percent by Weight of said repeating units.

20; 3. The polymeric composition of claim 2 in which said repeating unithasthe formula 8 The polymeric composition of claim 2 in which said repeating unit has the formula CHz(3- (CH3 COOOHzClLCHzN hnooon 2 No references cited.

JOSEPH L. SCHOFER, Primary Examiner.

HARRY WONG, JR., Assistant Examiner. 

